Diisopropyl-dithiophosphatyl thioketals



United States Patent 3,263,000 DIESOPROPYL-DITHIOPHOSPHATYL THIOKETALS Henryk A. Cyba, Chicago, Ill., assignor to Universal Oil Products Company, Des Plaines, Ill, a corporation of Delaware N0 Drawing. Filed Nov. 19, 1962, Ser. No. 238,773 3 Claims. (Cl. 260-929) This application relates to a novel composition of matter and to the use thereof.

The novel composition of matter of the present invention is selected from the group consisting of alpha-substituted dithiophosphatyl ketone, ketal and thioketal derivatives thereof.

The alpha-substituted dithiophosphatyl ketone is represented by the following formula:

where O is oxygen, S is sulfur, P is phosphorus, C is carbon, R and R are selected from the group consisting of hydrogen and hydrocarbon, R is selected from the group consisting of hydrogen, hydrocarbon, halogen and dithiophospha-tyl and X is selected from the group consisting of hydrogen and halogen.

The ketal and thioketal derivatives of the alpha-substituted dithiophosphatyl ketone are represented by the following formula:

where R, R, R and X have the same connotations as hereinbefore set forth, Y is selected from the group consisting of oxygen and sulfur, and R is selected from the group consisting of hydrogen and hydrocarbon.

Where R, R, R" and/or R' in the above formulas are hydrocarbon, they preferably are alkyl groups and more particularly alkyl groups of from 1 and still more particularly from 3 to 20 carbon atoms each. Other hydrocarbon groups included in the present invention are cycloalkyl and more particularly cyclopentyl and cyclohexyl, alkaryl and more particularly alkylphenyl and alkylnaphthyl in which the alkyl group contains from 1 to 20 carbon atoms, aryl and more particularly phenyl and naphthyl, aralkyl and more particularly phenylalkyl and naphthylalkyl in which the alkyl contains from 1 to 20 and still more particularly from 1 to 6 carbon atoms, alkylcycloalkyl and cycloalkylalkyl in which the alkyl contains from 1 to 20 carbon atoms, etc. It is understood that these groups, in turn, may contain non-hydrocarbon substituents attached thereto and particularly substituents containing halogen and more particularly chlorine, sulfur, oxygen, nitrogen, phosphorus, or mixtures thereof.

Referring to the first formula above set forth, in one preferred embodiment of the invention R and R are alkyl groups of from 1 to 20 and more preferably from 3 to carbon atoms, X is hydrogen and R is 3,263,660 Fatented July 26, 1966 hydrogen or an alkyl group of from 1 to 6 carbon atoms, or R is a dithiophosphatyl group and more particularly the same as the other dithiophosphatyl group.

Referring to the second formula above set forth, in one preferred embodiment of the invention R and R are alkyl groups of from 1 to 20 and preferably from 3 to 15 carbon atoms, at least one X is chlorine, Y is sulfur and R is an alkyl group of from 1 to 6 carbon atoms or R is a dithiophosphatyl group and more particularly the same as the other dithiophosphatyl group, and R is an alkyl group of from 1 to 6 carbon atoms.

The novel compounds of the present invention are readily prepared by the reaction of an alkali metal dithiophosphate and an alpha-haloketone in the presence of an oxygen-containing polar solvent. It is essential that the reaction is eifected in the presence of the polar solvent in order to form the novel compounds of the present invention by the interaction of the alkali metal component of the dithiophosphate with the halogen component of the haloketone. When using a non-polar solvent, entirely different reaction products may be obtained, apparently constituing an addition-type reaction in which both the alkali metal and the halogen are retained in the final product.

It also is essential that the haloketone used in preparing the novel composition of the present invention is an alpha-haloketone. In other words, at least one halogen should be positioned on the carbon atom adjacent to the keto group.

In a preferred embodiment the alpha-haloketone is an alpha-chloroketone. Preferred alpha-chloroketones include alpha-chloroketone (monochloroketone) and dichloroketone. In another embodiment the chloroketone comprises trichloroketone, tetrachloroketone or hexachloroketone. While the chloroketones are preferred, it is understood that the corresponding bromoketones, iodoketones and fluoroketones may be used.

Preferred alpha-chloroketones are chloroacetone, 1,3- dichloroacetone and hexachloroaeetone. Other chloroketones include l-chloro-butanone-Z, 1,3-dichlorobutanone-2, 1,4-dichlorobutanone-2, l-chloropentanone-Z,

1,3 -dichloropentanone-2, 1,4-dichloropentanone-2, 1,5 -dichloropentano11e-2 l-chlorohexanone-Z,

1 ,3-dichloroheXanone-2, 1,4-dichlorohexanone-2,

. 1,5-dichlorohexanone-2,

1,6-dich1oroheXanone-2, etc.

1,1-dichloroacetone, 1,1,3-trichloroacetone, 1,1,3,3-tetrachloroacetone, 1,1,1,3,3-pentachloroacetone, 1,1,1,3,3,3-hexachloroacetone, 1,1,3-trichlorobutanone-2,

,3,3 -tetrachlorobutanone-2, ,4-trichlorobutai1one-2,

1,1,4,4-tetrachlorobutanone-Z, 1,3,4-trichlorobutanone-2, 1,1,3,4-tetrachlorobutanone-2, 1,1,3,4,4-pentachlorobutanone-Z, 1,1,1,3,3,4,4,4-octachlorobutanone-2, 1,1,3-trichloropentanone-2, 1,1,3,3-tetrachloropentanone-2, 1,1,4-trich1oropentanone-2, 1,1,4,4-tetrachloropentanone-2, 1,1,S-trichloropentanone-Z, 1,1,5 ,5-tetrachloropentanone-2, 1 ,3,4,5-tetrachloropentanone-2, 1,1,3,4,5-pentachloropentanone-2,

l,1,3,3,4,4,5,5,5-decachloropentanone-2, ,1-dichlorohexanone-2, ,1 ,3-tric-hlorohexanone-2, ,1,3,3-tetrachlorohexanone-2, ,1 ,4-trichlorohexanone-2,

1,4,4-tetrachlorohexanone-Z, ,1 ,S-trichlorohexanone-Z,

1,5 ,5 -tetrachlorohexanone-2, ,1,6-trichlorohexanone-2, ,1,6,6-tetrachlorohexanone-2, 3,4,5 -tetrachlorohexanone-2, ,1,5,6-tetrachlorohexanone-Z, etc.

For economic reasons, sodium or potassium is preferred as the alkali metal component, although it is understood that lithium, calcium, magnesium, zinc, cadmium, barium, nickel, copper, etc., may be used. The reaction is readily effected by refluxing the alkali metal salt of the dithiophosphate and the haloketone in the presence of the oxygen-containing polar solvent.

When the haloketone is reacted with sodium or potassium dithiophosphoric acid, R in the first formula above set forth is hydrogen and the resultant compounds include d'ithiophosphatyl acetone [which also may be named S-(propyl-Z-one) dithiophosphate], dithiophosphatyl butanone-2, dithiophosphatyl pentanone-Z, dithiophosphatyl hexanone-Z, etc. In a preferred embodiment the dithiophosphatyl component preferably contains 1 or 2 alkyl groups, each containing from about 1 to about 20 carbon atoms. Illustrative compounds formed by the reaction of chloroketones with such dialkyl dithiophosphates include 0,0-dimethyhdithiophosphatyl acetone which also may be named 0,0-dimethyl-S-propyl-2-one-dithiophos phate, 0,0-diethyl-dithiophosphatyl acetone, 0,0-dimethyl-dithiophosphatyl-butanone-2, 0,0-diethyl-dithiophosphatyl-butanone-2, 0,0-dimethyl-dithiophosphatyl-pentanone-2, 0,0-diethyl-di-thiophosphatyl-pentanone-2, 0,0-dimethyl-dithiophosphatyl-hexanone-Z, O,-Odiethyl-dithiophosphatyl-hexanone-2, etc.

When used as an additive in lubricating oil, higher alkyl derivatives are preferred such as 4 0,0dieiscosyl-dithiophosphatyl acetone, etc., and similarly substituted dialkyl dithiophosphatyl butanone- 2, pentanone-Z, hexanone-2, etc.

Generally the alkyl groups are the same as in the compounds specifically set forth above, although it is understood that different alkyl groups may be used as illustrated, for example, in com-pounds as O-methyl-O-ethyl-dithiophosphatyl acetone, 0ethyl-O-propyl-dithiophosphatyl acetone, O-propyl-O-butyl-dithiophosphatyl acetone, O-propyl-O-amyl-dithiophosphatyl acetone, O-isopropyl-O-decyl-dithiophosphatyl acetone, O-isopropyl-O-tridecyl-dithiophosphatyl acetone, O-isopropyl-O-pentadecyl-dithiophosphatyl acetone, O-sec-butyl-O-octyl-dithiophosphatyl acetone, O-sec-butylO-decyl-dithiophosphatyl acetone, O-sec butyl-O-tridecyl-dithiophosphatyl acetone, O-sec-amyl-O-octyl-dithiophosphatyl acetone, O-sec-amyl-O-decyl-dithiophosphatyl acetone, O-sec-amyl-O-tridecyl-dithiophosphatyl acetone, etc.

The above specific compounds are examples of products obtained when the dithiophosphate is reacted in equal molar proportions with amonoohloroketone. When the dithiophosphate is reacted in a proportion of 2 moles of dithiophosphate to 1 mole of 1,3-dichloroacetone, R" in the first formula above set forth is a dithiophosphatyl group. Illustrative compounds in this embodiment include 1,3-bis-(0,0-dimethyl-dithiophosphatyl) acetone, 1,3-bis-(0,0-diethyl-dithiophosphatyl) acetone, 1,3-bis-(0,0-dipropyl-dithiophosphatyl) acetone, 1,3-bis-(0,0-dibutyl-dithiophosphatyl) acetone, 1,3-bis-(0,0-diphenyl-dithiophosphatyl) acetone, 1,3-bis-(0,0-dihexyl-dithiophosphatyl) acetone, 1,3-bis-(0,0-diheptyl-dithiophosphatyl) acetone, 1,3-bis-(0,0-dioctyl-dithiophosphatyl) acetone, 1,3-bis-(0,0-dinonyl-dithiophosphatyl) acetone, 1,3-bis-(0,0-didecyl-dithiophosphatyl) acetone, 1,3-bis(0,0-diundecyl-dithiophosphatyl) acetone, 1,3-bis-(0,0-did0decyl-dithiophosphatyl) acetone, 1,3-bis-(0,0-ditridecyl-dithiophosphatyl) acetone, etc., and the corresponding bis-(dialkyl-dithiophosphatyl) butanone-2, pentanone-Z, hexanone-2, etc.

The specific compounds hereinbefore set forth comprise those in Which the dithiophosphate contains two alkyl groups. It is understood that corresponding dithiophosphatyl compounds containing only one alkyl group attached to the phosphorus may be employed, in which embodiment the alkyl group is selected from those hereinbefore specifically set forth. Mixtures of the monoand di-alkyl phosphates are available commercially and conveniently are used in accordance with the present invention.

When the novel compound of the present invention is to be used as an additive to a hydrocarbon substrate, X in the above general formulas preferably is hydrogen. However, when these compounds are to be used as insecticides, pesticides, herbicides, rodenticides, etc., at least one X is a halogen and preferably chlorine. Illustrative compounds in this embodiment include Dialkyl-dithiophosphatyl-l-chloroacetone [which also may be named 0,0-dialkyl-S-( l-halopropyl-Z-one) dithiophosphate],

Dialkyl-dithiophosphatyl-1, l-dichloroacetone,

Dialkyl-dithiophosphatyl-3-chloroacetone,

Dialkyl-dithiophosphatyl-1,3-dichloroacetone,

Dialkyl-dithiophosphatyl-1,1,3,3,3-pentachloroacetone,

Dialkyl-dithiophosphatyl-l-chlorobutanone-Z,

Dialkyl-dithiophosphatyl-l,l-dichlorobutanone-Z,

Dialkyl-dithiophosphatyl-1,3-dichlorobutanone-2,

Dialkyl-dithiophosphatyl-1,4-dichlorobutanone-2,

Dialkyl-dithiophosphatyl-l-chloropentanone-Z,

Dialkyl-dithiophosphatyl-1,1-dichloropentanone-2,

Dialkyl-dithiophosphatyl-l-chlorohexanone-Z,

Dialkyl-dithiophosphatyl-l,l-dichlorohexanone-Z, etc., 1,3-bis-(0,0-dialkyl-dithiophosphatyl)-l-chloroacetone, 1,3-bis-(0,0-dialkyl-dithiophosphatyl)-l,1-dichloroacetone, 1,3-bis-(0,0-dialkyl-dithiophosphatyl)-1,1,3,3-tetrachloroacetone, 1,3-bis- (0,0-dialkyl-dithiophosphatyl) l-chlorobutanone-Z, 1,3-bis-(0,0-dialkyl-dithiophosphatyl)-1,1-dichlorobutanone-2, 1,3bis-(0,0-dialkyl-dithiophosphatyl)-1-chloropentanone-2, 1,3-bis-(0,0-dialkyl-dithiophosphatyl)-l,1-dichloropentanone-2, 1,3-bis-(0,0-dialkyl-dithiophosphatyl)-1-chlorohexanone-Z, 1,3-bis-(0,0-dialkyl-dithiophosphatyl)-l,l-dichlorohexanone-Z, etc.,

in which the alkyl groups contain from 1 to 20 carbon atoms each.

The alpha-substituted dithiophosphatyl ketones are prepared in any suitable manner and are readily prepared by the reaction of an alkali metal dithiophosphate with the haloketone. As hereinbefore set forth, when R" in the above formulas is hydrogen or an alkyl group, the dithiophosphate and haloketone are reacted in equal molar proportions. When R" in the above formulas is a dithiophosphatyl group, 2 mole proportions of the dithiophosphate are reacted per 1 mole proportion of the haloketone. The reaction is readily effected by refluxing the reactants for a time sufiicient to accomplish the desired reaction. This may range from 0.5 to 48 hours or more and generally will be for a time of from about 3 to about 20 hours. The refluxing temperature generally will be within the range of from about 30 to about 150 C. and preferably about 50 to about 100 C. The pressure may range from atmosphere to 1000 p.s.i.g. or more.

As hereinbefore set forth, it is essential that the reaction is effected in the presence of a polar solvent. Any suitable oxygen-containing polar solvent is employed including alcohols, particularly methanol, ethanol, propanol, butanol, etc., ketones including acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, etc., and glycols, glycolethers, alkylamides, dimethylformamide, dimethylacetamide, nitromethane, dimethyl or diethyl sulfoxide, dimethyl ether, diethyl ether, etc., water or aqueous solutions of the solvents hereinbefore set forth. When desired, either or both of the reactants may be prepared as a solution in the solvent for ease of handling or in forming a more fluid reaction mixture, or the solvent may be added to the reaction mixture. The solvent permits effecting the reaction at lower temperature and thereby favors the formation of monomers. Polymers are formed at the higher temperatures. The polymers or polycondensates are not harmful in lubricating oils, but are undesirable in pesticidal and insecticidal formulations.

In one method of operation the haloketone and alkali metal dialkyldith-iophosphate are formed as separate solutions in an alcoholic solvent. The solutions then are mixed, and the mixture is heated and maintained at refluxing conditions for the desired time. Following the completion of the reaction, the desired product is recovered in any suit-able manner. In one method the product is dissolved in an aromatic solvent, washed with water and/or sodium bicarbonate onsimilar solution, dried over anhydrous sodium sulfate, anhydrous potassium carbonate or the like, and then filtered and heated to remove the aromatic solvent, the latter generally being effected under vacuum.

As hereinbefore set forth, another embodiment of the invention comprises the ketal and thioketal derivatives of the alpha-substituted dithiophosphatyl ketone as illustrated by the second formula hereinbefore set forth. These derivatives may be prepared in any suitable manner and preferably by reacting the desired alcohol or'mercaptan with the alpha-substituted dithiophosphatyl ketone in the presence of an acid catalyst. Any suitable acid catalyst maybe used, hydrogen chloride being particularly preferred. In one embodiment the alcohol or mercaptan is used in a proportion of 2 moles thereof to 1 mole of the dithiophosphatyl ketone and in another embodiment the alcohol or mercaptan is used in equal mole proportions to the dithiophosphatyl ketone. The reaction readily occurs at ambient temperature by commingling the reactants, preferably with stirring, in order to obtain intimate mixing. Usually a slight excess of the alcohol or mencaptan is employed. Following completion of the reaction, the product is dried in any suitable manner, including the use of anhydrous sodium sulfate, anhydrous potassium carbonate, etc., and then filtered and distilled, preferably under vacuum, to remove lighter materials.

Any suitable alcohol is used, including methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol, etc. Similarly, any suitable mercaptan is used including methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, pentyl mercaptan, hexyl mercaptan, etc., benzylmercapt-an, th-iophenol or thiophenol derivatives as chlorothiophenol, para-nitrothiophenol, ortho-nitrothiophenol, 2 chloroethylmercaptan, 2 alkoxymercaptan and, in general, mercaptans containing such substituents as C], OH, RO, N0 etc.

Illustrative examples of the thioketal derivatives include Dialkyl-dithiophosphatyl-Z,Z-methylmercaptopropane, Dialkyl-dithiophosphatyl-2,2-ethylmencaptopropane, Dialkyl-dithiophosphatyl-2,2-propylmercaptopropane, Dialkyl-dithiophosphatyl-Z,2-butylmercaptopropane, Dialkyl-dithiophosphatyl-2,2-pentylmercaptopropane, Dialkyl-dithiophosphatyl-2,2-hexylmercaptopropane, etc., Dialkyl-dithiophosphatyl-2,Z-methylmercaptobutane, Dialkyl-dithiophosphatyl-2,2-ethylmercaptobut-ane, Dialkyl-dithiophosphatyl-2,Z-propylmercaptobutane, Dialkyl-dithiophosphatyl-2,2-butylmercaptobutane, Dialkyl-dithiophosphatyl-2,2-pentylmercaptobutane, Dialkyl-dithiophosphatyl-2,2-hexylmercaptobutane, etc., Dialkyl-dith-iophosphatyl-Z,2-methylmercaptopentane, Dialkyl-dithiophosphatyl-Z,Z-ethylmercaptopentane, Dialkyl-dithiophosphatyl-Z,2-propylmercaptopentane, Dialkyl-dithiophosphatyl-Z,Z-butylmercaptopentane, Dialkyl dithiophosphatyl-Z,2-pentylmercaptopentane, Dialkyl-dithiophosphatyl-2,2-hexylmercaptopentane, etc., Dialkyl-dithiophosphatyl-2,Z-methylmercaptohexane, Dialkyl-dith-iophosphatyl-2,2-ethylmercaptohexane, Dialkyl-dithiophosphatyl-2,2-propylmercaptohexane, Dialkyl-dithiophosphatyl-2,2-butylmencaptohexane, Dialkyl-dithiophosphatyl-2,Z-pentylmercaptohexane, Dialkyl-dithiophosphatyl-2,2-hexylmercaptohexane, etc., Dialkyl-dithiophosphatyl-1-chloro-2,2-dimethylmercaptopropane, Dialkyl-dithiophosphatyl-2,2-dimethylmercapto-3- chloropropane, Dialkyl-dithiophosphatyl-1,1-dichloro-2,2-dimethylmercaptopropane, Dialkyl-dithiophosphatyl-1,1,3-trichloro-2,2-dimethylmercaptopropane, Dialkyl-dithiophosphatyl-1,1,3,3-tetrachloro-dimethylmercaptopropane, Dialkyl-dithiophosphatyll 1,3 ,3,3 -pentachloro-dialkylmercaptopropane, etc.,

and similar substituted compounds in which the methylmercapto substituent is replaced by ethylmercapto, propylmercapto, butylmercapto, pentylmercapto, or hexylmercapto, as well as similarly substituted butanes, pentanes, hexanes, etc. Other illustrative examples include 1,3-bis- (dialkyl-dithiophosphatyl) -2,2-dimercaptopropane,

. 1,5 -bis-. (dialkyl-dithiphosphatyl)r2,2-dimercaptohexane,

1,6-bis-(dialkyl-dithiophosphatyl) -2,2-dimercaptohexane, etc.,

1,3-bis-(dialkyl-dithiophosphatyl) -1-chloro-2,2-mercaptopropane,

1,3-bis-(dialkyl-dithiophosphatyl)-1,1-dichloro-2,2-

mercaptoprop ane,

1,3-bis-(dialkyl-dithiophosphatyl) -1,3 -dichloro-2,2-

mercaptopropane,

1,3-bis-(dialkyl-dithiophosphatyl) -1,1,3 -trichloro-2,2- mercaptopropane,

1,3-bis-(dialkyl-dithiophosphatyl) -1,1,3 ,3 -tetrachloro- 2,2-mercaptopropane,

1,3-bis- (dialkyl-dithiophosphatyl -l l ,3,3-tetrachloro- 2,2-dialkylmercaptopropane, etc.,

and similarly substituted dithiophosphatyl butanes, pentanes, hexanes, etc. In another embodiment only one mercapto substituent is attached to the No. 2 carbon atom and these compounds will correspond to those hereinbefore specifically set forth, except for the single mercapto group.

The ketal derivatives will correspond to the thioketal derivatives hereinbefore set forth, except that the mercapto group will be replaced by an alkoxy group as illustrated, for example, in compounds as Dialkyl-dithiophosphatyl-2-methoxypropane, Dialkyl-dithiophosphatyl-Z-ethoxypropane, Dialkyl-dithiophosphatyl-Z-propoxypropane, Dialkyl-dithiophosphatyl-2-butoxypropane, etc., Dialkyl-dithiophosphatyl-2,Z-dimethoxypropane, Dialkyl-dithiophosphatyl-2,Z-diethoxypropane, Dialkyl-dithiophosphatyl-2,2-dipropoxypropane, Dialkyl-dithiophosphatyl-2,2-dibutoxypropane, etc., Dialkyl-dithiophosphatyl-1-chloro-2-methoxypropane, Dialkyl-dithiophosphatyl-l,l-dichloro-Z-methoxypropane, Dialkyl-dithophosphatyl-1,3-dichloro-2-methoxypropane, Dialkyl-dithiophosphatyl-l,1,3-trichloro-2-methoxypropane, Dialkyl-dithiophosphatyl-1,1,3,3-tetrachloro-2-meth0xypropane, Dialkyl-dithiophosphatyl-1,1,3,3,3-pentachloro-2,2-

dimethoxypropane, Dialkyl-dithiophosphatyl-l,l,3,3,3-pentochloro-2,2-

diethoxypropane, etc., 1,3-bis- (dialkyl-dithiophosphatyl) -2-methoxypropane, 1,3-bis- (dialkyl-dithiophosphatyl) -2,2-dimet'hoxypropane, 1,3-bis-( dialkyl-dithiophosphatyl) l-chloro-2-methoxypropane, 1,3-bis-(dialkyl-dithiophosphatyl) -1-chloro-2,2-

dimethoxypropane, 1,3-bis-(dialkyl-dithiophosphatyl)-l,1-dichloro-2,2-

dimethoxypropane, 1,3-bis-(dialkyl-dithiophosphatyl)-1,3-dichloro-2,2-

dimethoxypropane,

8 1,3-bis-(dialkyl-dithiophosphatyl) -1,l,3 -trichloro-2,2-

dimethoxyprop ane, 1 ,3-bis- (dialkyl-dithiophosphatyl) -1 ,l ,3 ,3-tetrachloro- 2,2-dimethoxypropane, etc.,

as well as correspondingly substituted dithiophosphatyl butanes, pentanes, hexanes, etc. It is understood that these are illustrative examples and that the alkyl groups will be selected from those hereinbefore specifically set forth and that other modifications within this class of compounds are included within the broad scope of the present invention.

From the hereinbefore description, it will be seen that a large number of novel compounds are comprised within the present invention. It is understood that these different compounds are not necessarily equivalent and that certain compounds will be more effective for certain uses. In general, as hereinbefore set forth, the halogen substituted compounds are desired for use as insecticides, pesticides, herbicides, rodenticides, etc., whereas the compounds free from halogen are preferred for use as additives to hydrocarbon substrates.

As hereinbefore set forth, the novel compounds of the present invention posses insecticidal properties with good inner-therapeutic action. They may be employed against many types of mites and insects such as, for example, Corausius larvae, Cotoneaster aphid, apple aphid, black bean aphid, aster aphid, green peach aphid, Chrysanthemum aphid, pea aphid, ets. The compounds or mixture of these may be used for the control of various larvae, mites, eggs of mites and such insects as flour beetle, Mexican bean beetle, black carpet beetle, milkweed bug, German cock-roaches, southern armyworms, mealy bug, sow bug, citrus red spider, greenhouse red spider, various mosquitoes, yellow fever mosquito, malarial mosquito, housefiies, etc.

The novel composition of matter of the present invention is particularly useful as an additive to hydrocarbon oil and still more particularly to lubricating oil. In the latter oil, the compound serves a number of important functions such as oxidation inhibitor (peroxide decomposer), bearing corrosion inhibitor, ring anti-plugging ad ditive, extreme pressure additive, anti-friction additive, pour point depressant, viscosity index improver, detergent, etc.

The lubricating oil may be straight mineral lubricating oil derived from parafiinic, naphthenic, asphaltic or mixed base petroleum crudes or blends thereof and is generally highly refined. In another embodiment the lubricating oil is a synthetic lubricating oil and may be one or a mixture of various types including aliphatic esters, polyalkylene oxides, silicones, esters of phosphoric and silicic acids, highly fluorine-substituted hydrocarbons, etc. Of the aliphatic esters, di-(Z-ethylhexyl) sebacate is being used on a comparatively large commercial scale.

'Ot-her aliphatic esters include dialkyl azelates, dialkyl suberates, dialkyl pimelates, dialkyl adipates, dialkyl glutarates, etc. Specific examples of these esters include dihexyl azelate, di-(Z-ethylhexyl) azelate, di-3,5,5-trimethyl glutarate, di-3,5,5-trimethylpentyl glutarate, di-(2- ethylhexyl) pimelate, di-(Z-ethylhexyl) adipate, triamyl tricarballylate, pentaerythritol tetracaproate, dipropylene glycol dipelargonate, 1,S-pentanediol-di-(Z-ethylhexanoate), etc. The polyalkylene oxides and derivatives include polyisopropylene oxide, polyisopropylene oxide diether, polyisopropylene oxide diester, etc. The silicones includes methyl silicone, methylphenyl silicone, etc., and the silicates include, for example, tetraisooctyl silicate, etc. Synthetic lubricants proposed for use in high temperature service as, for example, jet fuel lubrication, are pentaerythritol esters and trimethylol propane esters.

The novel composition of the present invention also is useful as an additive to lubricating greases. These may be either of synthetic or petroleum origin. The synthetic greases generally are referred to as lithium base grease, sodium base grease, calcium base grease, barium base grease, strontium base grease, aluminum base grease, mixed base greases including barium-calcium base grease, aluminum-calcium base grease, lithium-strontium base grease, etc. These greases are solid or semi-solid gels and, in general, are prepared by the addition to mineral or synthetic lubricating oils of hydrocarbon-soluble metal soaps or salts of higher fatty acids as, for example, lithium stearate, calcium stearate, aluminum naphthenate, etc. The grease may contain thickening agents such as silica, carbon black, polyacrylates, talc, etc. Another type of grease is prepared from oxidized petroleum wax, to which the saponifiable base is combined with the proper amount of the desired saponifying agent, and the resultant mixture processed to produce a grease. Other types of greases in which the features of the present invention are usable include petroleum grease, whale grease, wool grease, etc., and those made from inedible fats, tallow, butchers waste, etc.

The novel composition also is useful in the stabilization of polyolefins and particularly polyethylene. The polyolefins preferably are of high molecular weight, usually having a molecular weight'above 1000 and extending into the hundreds of thousand range. Generally these are synthetically prepared. A typical example is the widely used polyethylene plastics. Other polyolefins include polypropenes, polybutenes, and polymers of higher molecular weight olefins. These may be of the high density, medium density or low density type. Polyethylene is utilized, for example, as thermoplastic molding or coating agent. Because of its high dielectric strength and its resistance to water, polyethylene is particularly advantageous for use as insulators or dielectrics in condensers and other similar electronic equipment. However, polyethylene is subject to attack by atmospheric oxygen, particularly at elevated temperatures, either in use or during manufacture, and this impairs the desirable properties thereof including, for example, a reduction in the desirable electric properties, gelation upon oxidation, etc.

Other organic substances which deteriorate in storage, during treatment and/or in use, include hydrocarbons, and particularly motor fuels such as unsaturated gasoline, blends of unsaturated and saturated gasolines, etc., as well as jet fuel, diesel oil, mineral oil, fuel oil, residual oil, drying oil, Waxes, resins, rubber, etc. These substances are adversely effected by oxygen, with the resultant formation of one or more of undesirable gum, sediment, discoloration, cracking, corrosion, and/ or other deleterious reactions.

When used as an additive to organic substrates, the novel compounds of the present invention may be utilized in a concentration of from about 0.001% to about 25% by weight of the organic substrate, although in some cases higher or lower concentrations may be employed. The exact concentration to be used will depend upon the particular substrate to be treated. In most cases concentrations from about 0.01% to about by Weight generally will be employed.

It is understood that the composition of the present invention may be used along with other additives incorporated in the organic substrate. For example, one or more of an additional additive including metal deactivator, dye, viscosity index improver, pour point depressant, anti-foaming additive, lubricity and extreme pressure additive, anti-scuffing additive, detergent, corrosion inhibitor, etc., may be incorporated in the substrate. When desired, the composition of the present invention may be prepared as a mixture with one or more of these other additives and marketed and/or incorporated in the substrate in this manner.

The composition of the present invention may be incorporated in the organic substrate in any suitable manner and at any suitable stage of preparation. When incorporated in a liquid substrate, the composition of matter is added thereto and intimately mixed by conventional means. When added to a solid or semi-solid substrate, the composition of the present invention preferably is added during the manufacture thereof in order to obtain intimate mixing. For example, in the manufacture of grease, the composition of the present invention may be added to one or more of the components of the grease prior to compositing and processing thereof, or it may be added to the mix at any time, preferably before final processing in order to obtain intimate mixing and dissolving thereof in the grease. In other cases, a solid substrate may be dipped, soaked, or immersed in the additive, or the latter may be sprayed, brushed or otherwise applied to the solid substrate.

The following examples are introduced to illustrate further the novelty and utility of the present invention but not with the intention of unduly limiting the same.

EXAMPLE I Diisoproptyl-dithiophosphatyl acetone (also named 0,0-diisopropyl-S-propyl-Z-one-dith iophosphate or 0,0- diisopropyl dithiophosphatyl-propane-Z-o-ne) was prepared as follows: 126 g. (0.5 mole) of potassium diisopropyldithiophosphate were dissolved in 200 g. of methanol and the mixture was refluxed. 47 g. (0.5 mole) of chloro-2-propanone were added dropwise to the refluxing mixture. The reaction mixture was refluxed for 6.5 hours, following which benzene solvent was added and the mixture then was filtered to remove potassium chloride and was washed with hot acetone-methanol. The product then was washed with water, dried over anhydrous sodium sulfate, filtered and heated on a steam bath under vacuum to remove benzene and any lighter dissolved materials. 125 g. of product were recovered, which corresponds to the theoretical yield of 134 g. The product is diisopropyl-dithiophosphatyl acetone having a boiling point of -106 C. at 0.3-0.35 mm.

Analysis:

Phosphorus Percent Found 11.0 Theory 11.48

Sulfur Found 23.3 Theory 23.7

EXAMPLE II 1,3-bis (0,0-diisopropyl-dithiophosphlatyl) propane- 2-one was prepared as follows: 25.4 g. (0.2 mole) of 1,3- dichloro-Z-propanone were added dropwise to a refluxing solution of 100.8 g. (0.4 mole) of potassium diisopropyldithiophosphate in 200 g. of Formula 30 alcohol (primarily methanol). Following completion of the reaction, the product was dissolved in benzene, washed with water, washed with a solution of sodium bicarbonate, water washed again, dried over anhydrous sodium sulfate, filtered and heated on a steam bath under vacuum to remove benzene and lighter materials. The final product was recovered in a yield of 84 g., which corresponds to the theoretical yield of 96.6 g. The product is 1,3-bis- (0,0-diisopropyl-dithiophosphatyl) -propane-2-one.

Analysis:

Phosphorus Percent Found 12.2 Theory 12.8

Sulfur- Found 25.6 Theory 26.5

EXAMPLE III 1,3 bis (0,0 ditridecyl dithiophosphatyl) propane-Z-one was prepared as follows: g. (0.3 mole) of 0,0 ditridecyl dithiophosphate were reacted with 19.5 g. of potassium hydroxide in 200 g. of Formula 30 alcohol to prepare the potassium salt. While refluxing this solution, 30 g. of chloroacetone were added dropwise and the refluxing continued for a total of hours. The precipitated potassium chloride was dissolved in Water and the product was extracted with benzene, washed twice with water, dried over anhydrous sodium sulfate, filtered, and the benzene and lighter materials removed by heating under vacuum on a steam bath. 1,3 bis- (0,0 ditridecyl dithiophosphatyl) propane 2 one was recovered as a dark amber oily liquid in a yield of 170 g.

EXAMPLE IV The thioketal derivative of (0,0 diisopropyl dithiophosphatyl) propane 2 one, prepared as described in Example I, was prepared by reacting 67.5 g. mole) of this dithiophosphatyl propanone 2 with 34 g. /2 mole) plus excess of ethyl mercaptan in the presence of anhydrous hydrogen chloride. The reactants were commingled at room temperature and an exothermic reaction resulted. An additional 34 g. of ethyl mercaptan were added to replace the loss due to evaporation. Following completion of the reaction, the product was dried over anhydrous sodium sulfate, filtered and distilled under vacuum on a steam bath. The yield of the desired product was 79 g.

Analysis: Phosphorus- Found Percent Sulfur Found 32.34 Theory 34.05

EXAMPLE V The ketal derivative of 1,3 bis (0,0 diisopropyldithiophosphatyl) propanone 2, prepared as described in Example II, isrprepared in substantially the same manner as described in Example IV, except that ethyl alcohol is used in place of ethyl mercaptan. The reactants are used in a proportion of 1 mole of the dithiophosphatyl propanone and 2 mole proportions of the ethyl alcohol. Following completion of the reaction, the product is dried, filtered and heated under vacuum to remove lighter materials.

EXAMPLE VI 1,3 bis (dithiophosphatyl) 1,3 dichloro propanone 2 is prepared by reacting 2 mole proportions of the sodium salt of dithiophosphoric acid with 1 mole proportion of 1,1,3,3-tetrachloroacetone under refluxing conditions in the presence of isopropanol solvent. Following completion of the reaction, the reaction mixture is dissolved in benzene, filtered, washed, dried and distilled under vacuum.

EXAMPLE VII 1,3 bis (0,0 dimethyl dithiophosphatyl) 1,1, 3,3 tetrachloro propanone 2 is prepared by reacting 2 mole proportions of the sodium salt of 0,0 dimethyldithiophosphate with 1 mole proportion of hexachloroacetone under refluxing conditions in the presence of isopropanol solvents. After the reaction is completed, the reaction mixture is dissolved in benzene, filtered, washed, dried and distilled under vacuum.

EXAMPLE VIII As hereinbefore set forth, the compounds of the present invention are particularly advantageous for use as additives to lubricating oil. The present example illustrates the effectiveness of the compounds of Examples I and IV as additives in a typical paraflinic-solvent extracted lubricating oil evaluated in a Lauson engine. For this series of tests the runs were continued for 115 hours, except for the control run without additive which was discontinued after 24 hours because of seizure occurring, using a jacket temperature of 210 F. and an oil temperature of 280 F. Pertinent results of these runs are reported in the following table:

From the data in the above table, it will be noted that the novel compounds of the present invention were very effective in reducing corrosion, as evidenced by the very low bearing weight losses in runs 2 and 3 as compared to run number 1 which was made in the absence of the additive. Also, the compounds were effective in preventing undesired changes in the lubricating oil, as evidenced by the neutralization number, saponiflcation number, percent pentane insolubles and viscosity.

EXAMPLE IX An evaluation similar to that described in Example VIII was made for the compound of Example 11. This run was made in the same manner as described in Example VII and the pertinent results are shown in the following table. For comparative purposes, the control run, made without additive, is repeated in the table.

Table 11 Run Number 1 2 Additive None 0.5% by weight of Example II product Bearing wt. loss, gms 2. 9021 0.0102 Use 0' Pentane insolubles, percent 5.16 0.27

Viscosity, SSU at F 742 341 Here again, the effectiveness of the compound of the present invention is demonstrated, both in reducing corrosion as evidenced by the bearing weight loss and in preventing deterioration of the oil as evidenced by the analysis of the used oil.

EXAMPLE X As hereinbefore set forth, the chlorine-containing di thiophosphatyl ketone is useful as an insecticide. An insecticidal composition is prepared by dissolving 1 g. of 1,3-bis-(dithiophosphatyl)-1,3-dichloro-propanone-2, prepared as described in Example VI, in 2 cc. of benzene and emulsifying the resultant solution with 100 cc. of water using Triton X-100 as the emulsifying agent. The resulting emulsion is sprayed into a cage containing houseflies and results in greater than 98% knockdown.

I claim as my invention:

1. Alpha-substituted diisopropyl-dithiophosphatyl thioketal of the following formula:

3,263,000 13 14 Where R is alkyl of from one to 6 carbon atoms and R 3. Diethylmercaptol of diisopropyl-dithiophosphatyl is selected from the group consisting of hydrogen, alkyl acetone having the formula: of from one to three carbon atoms, and

III CH3 H(|)-H I-I3C(|3 H(|J-H H s t 1 t f f"? H 1/ H 1 H *SP\ rho-c H-(|3I-I 6 CH3 H-(|]H (|)CH3 H CH3 References Cited by the Examiner UNITED STATES PATENTS 2. Diethylmercaptol of 1,3-bis-(0,0-diisopropyldithio- 2,736,706 2/1956 Morris 25246.6 phosphatyl)-propane-2-one having the formula: 2,733,203 2/ 1957 m t- 25246.6 2,786,009 3/1957 Pianfetti et al. 167-22 2,841,517 7/1958 Boon et a1. 167-22 2,906,769 9/1959 Slagh 260-461 f 2,910,501 10/1959 Dorken et a1 260-461 0H3 11-0-11 CH; 3,105,003 9/1963 Walsh et a1 260-461 X Inc- 0 11-041 /(:3CH3 OTHER REFERENCES H o s III s FII g 0 H OBrien et al.: J. Econ. Entomol., vol. 51, pp. 714- 71s 1958 i H 11 Q} CHARLES B. PARKER, Primary Examiner. H'C-C E F D. WYMAN, JOSEPH P. BRUST, Examine-rs. ENE-H CH3 L. G. XIARHOS, FRANK M. SIKORA,

Assistant Examiners. 

1. ALPHA-SUBSTITUTED DIISOPROPYL-DITHIOPHOSPHATYL THIOKETAL OF THE FOLLOWING FORMULA: 